Compositions containing a polycondensate comprising at least one polyurethane and/or polyurea unit and a silicone comprising at least one carboxylic function

ABSTRACT

The invention relates to hair compositions comprising, in a cosmetically acceptable medium, a polycondensate comprising at least one polyurethane and/or polyurea unit and a silicone comprising at least one carboxylic function. The invention is also directed towards a process for shaping or maintaining the hairstyle, comprising the use of these compositions, and to their use for the manufacture of hair products, in order to maintain or shape the hairstyle.

[0001] The invention relates to compositions, such as those for hairstyling, comprising, in a cosmetically acceptable medium, apolycondensate, such as a multiblock polymer, comprising at least onepolyurethane and/or polyurea unit and a silicone comprising at least onecarboxylic functional group. The invention is also directed towards aprocess for shaping or maintaining a hairstyle comprising the use ofthese compositions, and to their use for the manufacture of hairproducts, in order to maintain or shape the hairstyle.

[0002] Fixing of the hairstyle is an important element of styling whichcomprises maintaining the shape already given or in shaping the hair andfixing it simultaneously. Hair products for shaping and/or maintainingthe hairstyle which are the most common on the cosmetics market arespray compositions comprising a solution, usually an alcoholic oraqueous solution, and one or more materials, generally polymer resins(also known as fixing materials), the function of which is to form weldsbetween the hairs, as a mixture with various cosmetic adjuvants. Thissolution can be packaged, for example, in a suitable aerosol containerplaced under pressure using a propellant. The construction and operationof such aerosol containers is well known to those skilled in the art.

[0003] Compositions intended for fixing and/or maintaining the hairstylesometimes have the drawback of adversely affecting the cosmeticproperties of the hair. Thus, the hair can become coarse and lose itsnatural softness. Styling compositions are thus sought which fix and/ormaintain the hairstyle well while at the same time afford good cosmeticproperties.

[0004] Patent DE 195 41 326 discloses styling compositions distributedfrom an aerosol device, which contain, in an aqueous-alcoholic medium, apolymer containing polyurethane units as fixing polymer, and apropellant. These compositions, which are already satisfactory in termsof fixing of the hairstyle, can, however, be improved in particular asregards the cosmetic properties which they give to the hair.

[0005] The inventors have discovered that by combining certain siliconeswith a polycondensate containing at least one polyurethane and/orpolyurea unit, it is possible to satisfy the requirements mentionedabove.

[0006] The subject of the invention is thus a composition, such as ahair styling composition, comprising, in a cosmetically acceptablemedium, in relative proportions by weight relative to the total weightof the composition, from 0.1 to 20%, inclusive, of a polycondensatecomprising at least one sequence chosen from polyurethanes andpolyureas, characterized in that it also comprises from 0.01 to 20%,inclusive, of at least one silicone chosen from partially and totallyneutralized silicone compounds comprising at least one carboxylicfunctional group and salts thereof.

[0007] Another subject of the invention relates to a process for shapingor maintaining the hairstyle, comprising the use of this composition.

[0008] Yet another subject of the invention relates to the use of thiscomposition for the manufacture of hair compositions, in order tomaintain or fix the hairstyle.

[0009] Examples of polycondensates comprising at least one polyurethaneand/or polyurea compound according to the present invention include, butare not limited to, those described in patents EP 0,751,162, EP0,637,600, FR 2,743,297, and EP 0,648,485, all assigned to the presentassignee, as well as patents EP 0,656,021 and WO 94/03510 from thecompany BASF, and EP 0,619,111 from the company National Starch. Thedisclosures of these documents are specifically incorporated herein byreference.

[0010] The polycondensates used in accordance with the invention can besoluble in a cosmetically acceptable medium, in particular afterneutralization with an organic or inorganic base, or alternatively canform a dispersion in this medium. In the latter case, the dispersion cangenerally comprise at least 0.05% of surfactant, which allows thepolycondensate to form a dispersion and to be maintained in dispersion.

[0011] According to the invention, any type of surfactant can be used inthe dispersion, including a nonionic surfactant. In certain embodiments,the average size of the polycondensate particles in the dispersion isbetween 0.1 and 1 micron (micrometer), inclusive.

[0012] By way of example, the polycondensate can be formed by anarrangement of blocks, this arrangement being obtained in particularusing:

[0013] (1) at least one compound which contains at least two activehydrogen atoms per molecule;

[0014] (2) at least one diol containing at least one functional groupchosen from acid radicals and salts thereof; and

[0015] (3) at least one isocyanate chosen from di- and polyisocyanates.

[0016] Compound (1) can be chosen from diols, diamines, polyesterols,polyetherols.

[0017] In certain embodiments, compound (1) can be a linear polyethyleneand polypropylene glycol, in particular those which are obtained byreaction of ethylene oxide or propylene oxide with water or diethyleneor dipropylene glycol in the presence of sodium hydroxide as catalyst.These polyglycols generally have a molecular weight ranging from about600 to 20,000.

[0018] Other suitable organic compounds that can be used are those whichhave mercapto, amino, carboxyl, or hydroxyl groups. Among these, mentionmay be made more particularly of polyhydroxy compounds such as polyetherdiols, polyester diols, polyacetal diols, polyamide diols,polyesterpolyamide diols, poly(alkylene ether) diols, polythioetherdiols, and polycarbonate diols.

[0019] In certain embodiments, the polyether diols are the condensationproducts of ethylene oxide, of propylene oxide, or of tetrahydrofuran;their copolymerization or condensation products, which may be grafted orblocks, such as mixtures of condensates of ethylene oxide and propyleneoxide; and the products of polymerization 1 of olefins, at highpressure, with alkylene oxide condensates. Suitable polyethers areprepared, for example, by condensation of alkylene oxides and polyhydricalcohols, such as ethylene glycol, 1,2-propylene glycol, and1,4-butanediol.

[0020] The polyester diols, polyesteramides, and polyamide diols can besaturated and can be obtained, for example, from the reaction ofsaturated or unsaturated polycarboxylic acids with polyhydric alcohols,diamines, or polyamines. Adipic acid, succinic acid, phthalic acid,terephthalic acid, and maleic acid can be used, for example, to preparethese compounds. Polyhydric alcohols that are suitable for preparing thepolyesters include, but are not limited to, ethylene glycol,1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, and hexanediol.Amino alcohols, for example ethanolamine, can also be used. Diaminesthat are suitable for preparing the polyesteramides includeethylenediamine and hexamethylenediamine.

[0021] Suitable polyacetals can be prepared, for example, from1,4-butanediol or from hexanediol, and from formaldehyde. Suitablepolythioethers can be prepared, for example, by condensation reactionbetween thioglycols, either alone or in combination with other glycolssuch as ethylene glycol, 1,2-propylene glycol or with otherpolyhydroxylated compounds. Polyhydroxylated compounds alreadycontaining urea or urethane groups and natural polyols, which can befurther modified, for example castor oil and carbohydrates, can also beused.

[0022] In certain embodiments, compound (1) is a polyesterol, inparticular a polyester diol formed by the reaction of at least one(di)polyol (1_(a)) and at least one acid (1 _(b)). The (di)polyol(1_(a)) can be chosen from the group comprising neopentyl glycol,1,4-butanediol, hexanediol, ethylene glycol, diethylene glycol,propylene glycol, butylene glycol, neopentyl glycol, and(di)polyethylene glycol. The acid (1_(b)) can be chosen from the groupcomprising phthalic acid, isophthalic acid, adipic acid, and(poly)lactic acid.

[0023] A hydroxycarboxylic acid such as dimethylol-propanoic acid (DMPA)or a 2,2-hydroxymethylcarboxylic acid can be used as compound (2). Ingeneral, compound (2) is useful as a coupling block. In certainembodiments, compound (2) comprises at least onepoly((α-hydroxydiolcarboxylic)acid). In certain other embodiments,compound (2) comprises 2,2-di(hydroxy-methyl)acetic acid,2,2-dihydroxymethylpropionic acid, 2,2-dihydroxymethylbutyric acid, or2,2-dihydroxy-methylpentanoic acid.

[0024] The isocyanate compound (3) can be chosen from, but is notlimited to, hexamethylene diisocyanate, isophorone diisocyanate (IPDI),toluylene diisocyanate, diphenylmethane 4,4′-diisocyanate (DPMD),dicyclohexylmethane 4,4′-diisocyanate (DCMD), methylenebis(p-phenyl)diisocyanate, methylenebis(4-cyclohexyl isocyanate), isophoronediisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate,4,4′-diphenylmethane diisocyanate, 2,2′-dimethyl-4,4′-diphenylmethanediisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate,mixtures of 2,4- and 2,6-toluene diisocyanate,2,2′-dichloro-4,4′-diisocyanatodiphenylmethane,2,4-dibromo-1,5-diisocyanatonaphthalene, butane 1,4-diisocyanate,1,6-hexane diisocyanate, and 1,4-cyclohexane diisocyanate.

[0025] The polycondensate can be formed using at least one additionalcompound (4), which generally serves to extend the polycondensate chain.Examples of compounds ii suitable as compound (4) include, but are notlimited to, saturated or unsaturated glycols such as ethylene glycol,diethylene glycol, neopentyl glycol, or triethylene glycol; aminoalcohols such as ethanolamine, propanolamine or butanolamine;heterocyclic, aromatic, cycloaliphatic and aliphatic primary amines;diamines; carboxylic acids such as aliphatic, aromatic or heterocycliccarboxylic acids, for instance oxalic acid, succinic acid, glutaricacid, adipic acid, sebacic acid, or terephthalic acid; and aminocarboxylic acids. In certain embodiments, compound (4) is an aliphaticdiol.

[0026] The polycondensates in accordance with the invention can also beformed from at least one additional compound (5) having a siliconeskeleton. In certain embodiments, compound (5) is chosen frompolysiloxanes, polyalkylsiloxanes, and polyarylsiloxanes. In certainembodiments, compound (5) is a polyethylsiloxane, polymethylsiloxane, ora polyphenylsiloxane. For example, the polyalkylsiloxane can be chosenfrom polyethylsiloxanes or polymethylsiloxanes, and the polyarylsiloxanecan be chosen from polyphenylsiloxanes. Compound (5) can optionallycontain hydrocarbon-1 based chains grafted onto at least one siliconatom.

[0027] According to an embodiment of the compositions of the invention,the polyurethane and/or polyurea sequences of the polymer have arepeating base unit corresponding to the formula (I′):

—X′—B—X′—CO—NH—R—NH—CO—  (I′)

[0028] in which:

[0029] X′ is chosen from O and NH,

[0030] B is a divalent hydrocarbon-based radical, this radical beingsubstituted or unsubstituted, and

[0031] R is a divalent substituted or unsubstituted radical chosen fromaromatic alkylene radicals, C₁ to C₂₀ aliphatic radicals, and C₁ to C₂₀cycloaliphatic radicals.

[0032] In certain embodiments, radical B is a C₁ to C₃₀ radical andbears a group containing one or more carboxylic functional groups and/orone or more sulphonic functional groups, the carboxylic and/or sulphonicfunctional groups being in free form or else partially or totallyneutralized with an inorganic or organic base. In certain embodiments,radical B is a C₁ to C₃₀ divalent hydrocarbon-based radical.

[0033] The radical R is advantageously chosen from radicalscorresponding to the following formulae:

[0034] in which b is an integer between 0 and 3, inclusive, and c is aninteger between 1 and 20, inclusive, such as between 2 and 12,inclusive.

[0035] In certain embodiments, radical R is chosen from hexamethylene,4,4′-biphenylenemethane, 2,4- and/or 2,6-tolylene, 1,5-naphthylene,p-phenylene and methylene4,4-bis-cyclohexyl radicals, and divalentradicals derived from isophorone.

[0036] The polycondensate used in accordance with the inventioncomprising at least one polyurethane and/or polyurea compound or unitcan also comprise at least one polysiloxane compound in which therepeating base unit corresponds, for example, to the formula (II′):

—X′—P—X′—CO—NH—R—NH—CO—  (II′)

[0037] in which:

[0038] P is a polysiloxane segment,

[0039] X′ is chosen from O and NH, and

[0040] R is chosen from divalent substituted and unsubstituted radicalschosen from aromatic alkylene radicals, C₁ to C₂₀ aliphatic radicals,and C₁ to C₂₀ cycloaliphatic radicals.

[0041] In certain embodiments, the polysiloxane segment P corresponds tothe formula (III):

[0042] in which:

[0043] the radicals A, which can be identical or different, are chosenfrom, on the one hand, C₁ to C₂₀ monovalent hydrocarbon-based radicalswhich are free or substantially free of ethylenic unsaturation and, onthe other hand, aromatic radicals,

[0044] Y represents a divalent hydrocarbon-based radical, and

[0045] z represents an integer chosen such that the average molecularweight of the polysiloxane segment ranges from 300 to 10,000.

[0046] In general, the divalent radical Y is chosen from alkyleneradicals of formula —(CH₂)_(a)—, in which a represents an integer whichcan range from 1 to 10, inclusive.

[0047] The radicals A can be, but are not necessarily, chosen from alkylradicals, including methyl, ethyl, propyl, isopropyl, butyl, pentyl,hexyl, octyl, decyl, dodecyl and octadecyl radicals; cycloalkylradicals, such as the cyclohexyl radical; aryl radicals, includingphenyl and naphthyl; arylalkyl radicals, such as benzyl and phenylethyl;and tolyl and xylyl radicals.

[0048] The polycondensates used in accordance with the invention can besoluble in a cosmetically acceptable medium, in particular afterneutralization with an organic or inorganic base, or else can form adispersion in this medium. Generally, in the latter case, the dispersioncomprises at least 0.05% surfactant, which allows the polycondensate toform a dispersion and to be maintained in dispersion.

[0049] According to the invention, any type of surfactant can be used inthe dispersion, including a nonionic surfactant. The average size of thepolycondensate particles in the dispersion is generally between 0.1 and1 micron (micrometer), inclusive.

[0050] The composition in accordance with the invention generallycomprises, in relative proportions by weight relative to the totalweight of the composition, between 0.1 and 20%, inclusive, of thepolycondensate comprising at least one sequence chosen frompolyurethanes. In certain embodiments, the polycondensate comprises, ona weight-to-weight basis, between 1 and 15%, inclusive, of thecomposition. In certain embodiments, the polycondensate comprisesbetween 2 and 8%, inclusive, by weight, of the composition.

[0051] In certain embodiments, the silicones according to the presentinvention are those described in patent EP 0,756,860, in patentapplication WO 98/20833, and in the French patent application whoseapplication number is 97/16507, all assigned to the present assignee,and all of which are hereby incorporated by reference herein.

[0052] For the purposes of the present invention, the term silicone isunderstood to refer to any organosilicone polymer or oligomer of linearor cyclic, branched, or crosslinked structure, of variable molecularweight, obtained by polymerization and/or polycondensation of suitablyfunctionalized silanes comprising a repetition of the main Gi units inwhich silicon atoms are linked together by oxygen atoms to form asiloxane bond (≡Si—O—Si≡), with hydrocarbon-based radicals, which areoptionally substituted, being directly linked from a carbon atom to thesaid silicon atoms. The most common hydrocarbon-based radicals are thealkyl radicals, especially C₁-C₁₀ alkyl radicals and in particularmethyl, fluoroalkyl radicals, and aryl radicals and in particularphenyl.

[0053] According to a first embodiment of the compositions in accordancewith the invention, the silicone comprising at least one carboxylicfunctional group is an organopolysiloxane comprising at least one unitcorresponding to formula (I):

[0054] R₁ and R₃ independently are chosen from linear and branchedalkylene radicals having from 2 to 20 carbon atoms;

[0055] R₂ is chosen from linear and branched alkylene radicals havingfrom 1 to 50 carbon atoms and optionally comprising a hydroxyl group;

[0056] a represents 0 or 1;

[0057] b is a number ranging from 0 to 200; and

[0058] M is chosen from hydrogen, alkali metals and alkaline-earthmetals, NH₄, and quaternary ammonium groups such as, in particular,mono-, di-, tri- and tetra(C₁-C₄ alkyl)-ammonium groups.

[0059] It is possible, for example, to use organopolysiloxanescontaining carboxylic functions, corresponding to formula (II):

[0060] in which:

[0061] the radicals R₄ are identical or different and are chosen fromthe group comprising linear and branched C₁-C₂₂ alkyl radicals, C₁-C₂₂alkoxy radicals, and phenyl radicals,

[0062] the radicals R₅, R₆, and R₇ are identical or different and arechosen from the group comprising linear and branched C₁-C₂₂ alkylradicals, C₁-C₂₂ alkoxy radicals, phenyl-based radicals, and radicals(R₁O)_(a)—R₂—(OR₃)_(b)—COOM, with the restriction that at least one ofthe radicals R₅, R₆ or R₇ is a radical —(R₁₀)_(a)—R₂—(OR₃)_(b)—COOM,

[0063] the radicals R₁, R₂, R₃, a, b, and M have the same meanings as informula (I),

[0064] c and d are numbers ranging from 0 to 1000. In certainembodiments, the sum c+d ranges from 2 to 1000.

[0065] Among the silicones of formula (II), certain compounds are thosewhich satisfy formula (III):

[0066] in which X is a radical —(R₁O)_(a)—R₂—(OR₃)_(b)—COOM, theradicals R₁, R₂, R₃, a, b, d, and M having the same meanings as forformulae (I) and (II).

[0067] As compounds corresponding to formula (III), it is possible, forexample, to use those sold under the trade name Oil M 642, SLM 23 000/1or SLM 23 000/2 by the company Wacker, or alternatively under the tradename 176-12057 by the company General Electric, or alternatively underthe trade name FZ 3703 by the company OSI, or alternatively under thetrade name BY 16 880 by the company Toray Silicone.

[0068] According to a second embodiment of the compositions inaccordance with the invention, the silicone can be formed by a mainsilicone chain corresponding to the formula (≡Si—O—)_(n) onto which isgrafted, inside the chain as well as, optionally, on at least one of itsends, at least one hydrocarbon-based group comprising at least onecarboxylic functional group.

[0069] The nature and/or amount of the hydrocarbon-based groupscomprising at least one carboxylic functional group are chosen such thatthe corresponding silicone derivative is water-soluble orwater-dispersible, after optional neutralization of the groups ofanionic nature using an alkaline agent.

[0070] These specific silicone derivatives can be existing commercialproducts or alternatively can be obtained according to any means knownto those skilled in the art, in particular by reaction between (i) astarting silicone which is correctly functionalized on one or more ofthese silicon atoms, and (ii) an anionic compound which is itselfcorrectly functionalized with a functional group which is capable ofreacting with the functional group(s) borne by the silicone, to form acovalent bond. A standard example of such a reaction is thehydrosilylation reaction between ≡Si—H groups and vinylic l groupsCH₂═CH—, or alternatively the reaction between thio functional groups—SH with these same vinylic groups.

[0071] Examples of silicone derivatives comprising a main silicone chainon which is grafted, inside the said chain as well as, optionally, onits ends, at least one hydrocarbon-based group comprising at least onecarboxylic functional group, which are suitable for carrying out thepresent invention, along with their specific mode of preparation, aredescribed in particular in patent applications EP 0,582,152 and WO93/23009, the disclosures of which are specifically incorporated hereinby reference.

[0072] Silicone derivatives suitable for carrying out the presentinvention include those whose structure contains the following unit:

[0073] in which G₁ is chosen from hydrogen, C₁-C₁₀ alkyl radicals, andphenyl radicals; G₂ is chosen from C₁-C₁₀ alkylene groups; G₃ is chosenfrom anionic polymer residues resulting from the (homo)polymerization ofat least one anionic monomer containing ethylenic unsaturation; n isequal to 0 or 1; a is an integer which is between 1 and 50, inclusive;and b is an integer which is between 10 and 350, inclusive.

[0074] In certain embodiments, the unit of formula (IX) above has atleast one of the following characteristics:

[0075] G₁ is an alkyl radical, such as a methyl radical,

[0076] n is non-zero, and G₂ represents a C₁-C₃ divalent radical, suchas a propylene radical,

[0077] G₃ represents a polymer radical resulting from the(homo)polymerization of at least one monomer of unsaturated carboxylicacid type, such as acrylic acid and/or methacrylic acid.

[0078] In certain embodiments, the unit of formula (IX) above has all ofthe above characteristics.

[0079] In certain embodiments, the amount of carboxylate groups in thefinal polymer is between 1 mol of carboxylate per 200 g of polymer and 1mol of carboxylate per 5000 g of polymer, inclusive. In certainembodiments, the number-average molecular mass of the silicone polymeris between approximately 10,000 and approximately 1,000,000. In certainembodiments, the number-average molecular mass of the silicone polymeris between approximately 10,000 and 100,000.

[0080] Examples of silicone derivatives suitable for carrying out thepresent invention are, for example, those sold by the 3M company underthe trade name Silicone “plus” Polymer VS 80. These products correspondto polydimethylsiloxanes (PDMSs) onto which are grafted, via aconnecting chain of thiopropylene type, mixed polymer units ofpoly(meth)acrylic acid type and of polybutyl (meth)acrylate ester type.These products can be obtained conventionally by radicalcopolymerization between, on the one hand, a silicone ofpolydimethylsiloxane type prefunctionalized with thiopropyl groups, and,on the other hand, a monomer mixture consisting of (meth)acrylic acidand butyl (meth)acrylate.

[0081] Other silicones suitable for carrying out the present inventionare silicones comprising at least one substituent containing at leasttwo groups, which may be identical or different, chosen from carboxylicacids and salts thereof, amides, and esters, at least one of thesegroups being chosen from carboxylic acids and salts thereof.

[0082] In certain embodiments, these silicones comprise at least oneunit of formula (IV):

ZR_(a)SiO_((3-a)/2)  (IV)

[0083] in which Z is a radical corresponding to formula (V) below:

[0084] in which:

[0085] W, R₂, and R₄, which may be identical or different, are chosenfrom a covalent bond and linear and branched alkylene radicals havingfrom 1 to 6 carbon atoms which can comprise a hydroxyl group,

[0086] R₃ is chosen from a hydrogen atom and linear and branched C₁-C₆alkyl radicals,

[0087] X and X′, which may be identical or different, are chosen fromthe radicals OM, NR₅R₆, and OR₇,

[0088] M is chosen from a hydrogen atom; alkali metals (for example Na⁺,K⁺); NH₄ ⁺; ammonium groups containing a residue chosen from the groupcomprising basic amino acids such as lysine, arginine, sarcosine,ornithine and citrulline; and amino alcohols such as monoethanolamine,diethanolamine, triethanolamine, glucamine, N-methylglucamine, and3-amino-1,2-propanediol,

[0089] R₅ and R₆, which may be identical or different, are chosen fromthe group comprising hydrogen and linear and branched C₁-C₆ alkyls, oralternatively R₅ and R₆ can together form a 5- or 6-memberedheterocycle,

[0090] R₇ is chosen from linear and branched C₁-C₃₀ alkyl radicals, and

[0091] at least one of the groups X and X′ denotes OM.

[0092] In formula (IV), the radicals R, which may be identical ordifferent, are chosen from alkyl radicals, especially C₁-C₁₀ alkylradicals and in particular methyl, fluoroalkyl radicals, especiallyC₁-C₁₀ fluoroalkyl radicals, C₆-C₁₂ aryl radicals and in particularphenyl. In certain embodiments, a is chosen from 0, 1 and 2. In certainembodiments, a is 1 or 2. In certain embodiments, the radicals R offormula (IV) are chosen from C, to C₁₀ alkyl radicals, C₁ to C₁₀fluoroalkyl radicals, and C₆ to C₁₂ aryl radicals.

[0093] In certain embodiments, the silicones used comprise at least oneunit of formula (IV), which satisfy at least one of the followingconditions:

[0094] W denotes a covalent bond,

[0095] R₃ denotes a hydrogen atom,

[0096] R denotes a methyl radical,

[0097] X and X′ are chosen from OM and NR₅R₆,

[0098] R₂ and R₄, which may be identical or different, are chosen from acovalent bond and a methyl radical.

[0099] In certain embodiments, the silicones satisfy all of the aboveconditions.

[0100] The other units of the silicone can be chosen from those offormula (VI):

R_(b)SiO_((4-b)/2)  (VI)

[0101] in which R has the same meaning as in formula (IV) and b is equalto 0, 1, 2, or 3. In certain embodiments, b is equal to 2 or 3.

[0102] The silicones comprising at least one unit of formula (IV) aredescribed in particular in U.S. Pat. No. 4,931,062, the disclosure ofwhich is specifically incorporated herein by reference. Such siliconesare sold, for example, under the trade name SLM 23 105 by the companyWacker and under the trade name Densodrin OF by the company BASF.

[0103] The relative proportion by weight, relative to the total weightof the composition, of silicone or of silicone mixture is generallybetween 0.01 and 20%, inclusive. In certain embodiments, the relativeproportion is between 0.01 and 10%, inclusive. In certain embodiments,the relative proportion is between 0.05 and 5%, inclusive.

[0104] The composition in accordance with the invention can be, but doesnot have to be, in the form of a lotion or a gel. It can be applied, forexample, by spraying, such as from a pump-dispenser bottle or anaerosol.

[0105] The packaging in aerosol form is especially practical for theuser, who obtains fairly homogeneous distribution of the product withoutdifficulty. However, this type of packaging can have the drawback ofgiving rise to a release of volatile organic compounds (VOCs) that areharmful to the environment. They originate in particular from the amountof organic solvent used and of propellant gas chosen to manufacture thecomposition. Thus, the preparation of cosmetic compositions packaged inaerosol form for which the amount of volatile organic compounds expelledis low, is included within the invention and is well within the ordinaryskill in the art.

[0106] The quality of the spraying obtained by means of an aerosoldevice, i.e., essentially the distribution of the droplets in space atthe nozzle outlet, can depend greatly on the chemical constitution ofthe composition used. It is desired to formulate cosmetic compositionswhich give rise to an optimum quality of spraying.

[0107] Generally, between 7.5 and 70%, inclusive, of the total weight ofthe composition is comprised of an organic solvent. In certainembodiments, between 10 and 50%, inclusive, of the total weight of thecomposition is comprised of an organic solvent. In certain embodiments,between 10 and 25%, inclusive, of the total weight of the composition iscomprised of an organic solvent.

[0108] In accordance with the invention, the organic solvent can bechosen in particular from the group comprising C₁-C₄ lower alcohols suchas ethanol, isopropanol; acetone; methyl ethyl ketone; methyl acetate;butyl acetate; ethyl acetate; dimethoxyethane; diethoxyethane; andmixtures thereof. In certain embodiments, ethanol is used.

[0109] The composition of the invention generally comprises, in relativeproportions by weight relative to the total weight of the composition,between 15 and 85%, inclusive, of a propellant gas. In certainembodiments, the composition comprises between 25 and 60%, inclusive, ona weight-to-weight basis, of a propellant gas. In certain embodiments,the composition comprises between 30 and 50%, inclusive, on aweight-to-weight basis, of a propellant gas.

[0110] In accordance with the invention, a gas which is soluble orinsoluble in the composition, such as dimethyl ether, fluoro ornon-fluoro hydrocarbons, the usual liquefied gases used in body-treatingcompositions, or a mixture of these propellant gases can be used aspropellant gas. In certain embodiments, dimethyl ether is used.

[0111] The concentrations and the nature of the various components canbe chosen so as to reduce the contents of volatile organic compounds(VOCs).

[0112] The compositions in accordance with the invention can moreovercontain at least one cosmetic additive. Examples of such additivesinclude, but are not limited to, fatty substances, thickeners,softeners, antifoaming agents, moisturizers, antiperspirants, basifyingagents, dyes, pigments, fragrances, preserving agents, surfactants,hydrocarbon-based polymers, additional volatile and non-volatilesilicones other than those described above, proteins, and vitamins.

[0113] In particular, it may be advantageous to add fixing polymers tothe composition, such as nonionic, anionic, cationic, or amphotericfixing polymers.

[0114] A better understanding of the invention may be gained with theaid of the non-limiting example which follows and which constitutes anadvantageous embodiment of the compositions in accordance with theinvention.

EXAMPLE

[0115] The composition below, for which the percentages are relativepercentages by weight, is prepared.

[0116] Lactic acid/ethylene glycol P(MIS-EG)-dimethylolpropanoic acid(DMPA)-isophbrone-diisocyanate polyester polycondensate . . . 4%

[0117] Silicone “Plus” Polymer VS 80 . . . 0.2%

[0118] Aminomethylpropanol . . . qs neutralization

[0119] Ethanol . . . 15%

[0120] Dimethyl ether . . . 35%

[0121] Demineralized water . . . qs . . . 100%

What is claimed is:
 1. A hair composition comprising, in a cosmetically acceptable medium, in relative proportions by weight relative to the total weight of the composition, (a) from 0.1 to 20%, inclusive, of a polycondensate comprising at least one sequence chosen from polyurethanes and polyureas, (b) from 0.01 to 20%, inclusive, of at least one silicone chosen from partially and totally neutralized silicone compounds comprising at least one carboxylic functional group and salts thereof.
 2. The composition according to claim 1, wherein the polycondensate is formed by an arrangement of blocks obtained using: (1) at least one compound which contains at least two active hydrogen atoms per molecule; (2) at least one diol containing at least one functional group chosen from acid radicals and salts thereof; and (3) at least one isocyanate chosen from di- and polyisocyanates.
 3. The composition according to claim 2, wherein said at least one compound (1) is chosen from diols, diamines, polyesterols, and polyetherols.
 4. The composition according to claim 2, wherein said at least one diol (2) is a 2,2-hydroxymethylcarboxylic acid.
 5. The composition according to claim 2, wherein said at least one isocyanate (3) is chosen from hexamethylene diisocyanate, isophorone diisocyanate, toluylene diisocyanate, diphenylmethane 4,4′-diisocyanate, dicyclohexylmethane 4,4′-diisocyanate, methylenebis(p-phenyl) diisocyanate, methylenebis(4-cyclohexyl isocyanate), isophorone diisocvanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,2′-dimethyl-4,4′-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, 2,2′-dichloro-4,4′-diisocyanatodiphenylmethane, 2,4-dibromo-1,5-diisocyanatonaphthalene, butane 1,4-diisocyanate, 1,6-hexane diisocyanate, and 1,4-cyclohexane diisocyanate.
 6. The composition according to claim 2, wherein the polycondensate is formed from at least one additional compound having a silicone skeleton.
 7. The composition according to claim 6, wherein the at least one additional compound having a silicone skeleton is chosen from polysiloxanes, polyalkylsiloxanes, and polyarylsiloxanes, and wherein said polysiloxanes, polyalkylsiloxanes, and polyarylsiloxanes optionally contain hydrocarbon-based chains grafted onto at least one silicon atom.
 8. The composition according to claim 7, wherein the polyalkylsiloxane is chosen from polyethylsiloxanes or polymethylsiloxanes, and the polyarylsiloxane is chosen from polyphenyisiloxanes.
 9. The composition according to claim 1, wherein said at least one sequence chosen from polyurethanes and polyureas has a repeating base unit corresponding to the formula (I′): —X′—B—X′—CO—NH—R—NH—CO—  (I′) in which: X′ is chosen from O and NH, B is a divalent hydrocarbon-based radical, this radical being substituted or unsubstituted, and R is a divalent substituted or unsubstituted radical chosen from aromatic alkylene radicals, C₁ to C₂₀ aliphatic radicals, and C₁ to C₂₀ cycloaliphatic radicals.
 10. The composition according to claim 9, wherein B is a C₁ to C₃₀ divalent hydrocarbon-based radical.
 11. The composition according to claim 9, wherein radical R is chosen from hexamethylene, 4,4′-biphenylenemethane, 2,4-tolylene, 2,6-tolylene, 1,5-naphthylene, p-phenylene and methylene-4,4-bis-cyclohexyl radicals, and divalent radicals derived from isophorone.
 12. The composition according to claim 1, wherein the polycondensate has a repeating base unit corresponding to formula (II′): —X′—P—X′—CO—NH—R—NH—CO—  (II′) in which: P is a polysiloxane segment, X′ is chosen from O and NH, and R is chosen from divalent substituted and unsubstituted radicals chosen from aromatic alkylene radicals, C₁ to C₂₀ aliphatic radicals, and C₁ to C₂₀ cycloaliphatic radicals.
 13. The composition according to claim 1, wherein the silicone compound is an organopolysiloxane comprising at least one unit corresponding to formula (I):

in which: R₁ and R₃ independently are chosen from linear and branched alkylene radicals having from 2 to 20 carbon atoms; R₂ is chosen from linear and branched alkylene radicals having from 1 to 50 carbon atoms and optionally comprising a hydroxyl group; a represents 0 or 1; b is a number ranging from 0 to 200; and M is chosen from hydrogen, alkali metals, alkaline-earth metals, NH₄, and quaternary ammonium groups.
 14. The composition according to claim 13, wherein the quaternary ammonium group is chosen from mono-, di-, tri- and tetra(C₁-C₄ alkyl)-ammonium groups.
 15. The composition according to claim 1, wherein the silicone compound comprises a main chain corresponding to the formula (≡Si—O—)_(n) onto which is grafted, inside the chain as well as, optionally, on at least one of its ends, at least one hydrocarbon-based group comprising at least one carboxylic functional group.
 16. The composition according to claim 15, wherein the silicone compound comprises the unit (IX):

in which G₁ is chosen from hydrogen, C₁-C₁₀ alkyl radicals, and phenyl radicals; G₂ is chosen from C₁-C₁₀ alkylene groups; G₃ is chosen from anionic polymer residues resulting from the (homo)polymerization of at least one anionic monomer containing ethylenic unsaturation; n is equal to 0 or 1; a is an integer which is between 1 and 50, inclusive; and b is an integer which is between 10 and 350, inclusive.
 17. The composition according to claim 1, wherein the silicone compound comprises at least one unit of formula (IV): ZR_(a)SiO_((3-a)/2)  (IV) in which Z is a radical corresponding to formula (V):

in which: W, R₂, and R₄, which may be identical or different, are chosen from a covalent bond and linear and branched alkylene radicals having from 1 to 6 carbon atoms which can comprise a hydroxyl group, R₃ is chosen from a hydrogen atom and linear and branched C₁-C₆ alkyl radicals, X and X′, which may be identical or different, are chosen from the radicals OM, NR₅R₆, and OR₇, M is chosen from a hydrogen atom; alkali metals; NH₄ ⁺; ammonium groups containing a residue chosen from the group comprising basic amino acids; and amino alcohols, R₅ and R₆, which may be identical or different, are chosen from the group comprising hydrogen and linear and branched C₁-C₆ alkyls, or alternatively R₅ and R₆ can together form a 5- or 6-membered heterocycle, R₇ is chosen from linear and branched C₁-C₃₀ alkyl radicals, and at least one of the groups X and X′ denotes OM, wherein a is an integer equal to 0, 1 or
 2. 18. The composition according to claim 17, wherein the radicals R of formula (IV), which may be identical or different, are chosen from C₁ to C₁₀ alkyl radicals, C₁ to C₁₀ fluoroalkyl radicals, and C₆ to C₁₂ aryl radicals.
 19. The composition according to claim 1, wherein the relative proportion by weight of said at least one silicone is between 0.01 and 10%, inclusive.
 20. The composition according to claim 1, wherein the relative proportion by weight of said at least one silicone is between 0.05 and 5%, inclusive.
 21. The composition according to claim 1, comprising between 1 and 15%, inclusive, of said polycondensate, by weight of the total weight of the composition.
 22. The composition according to claim 21, comprising between 2 and 8%, inclusive, of said polycondensate, by weight of the total weight of the composition.
 23. A pump-dispenser bottle or an aerosol device comprising, in a cosmetically acceptable medium, in relative proportions by weight relative to the total weight of the composition, (a) from 0.1 to 20%, inclusive, of a polycondensate comprising at least one sequence chosen from polyurethanes and polyureas, (b) from 0.01 to 20%, inclusive, of at least one silicone chosen from partially and totally neutralized silicone compounds comprising at least one carboxylic functional group and salts thereof.
 24. The composition according to claim 1, further comprising: (i) an organic solvent in a relative concentration by weight of between 7.5 and 70%, inclusive, and (ii) a propellant gas in a relative concentration by weight of between 15 and 85%, inclusive.
 25. The composition according to claim 24, comprising between 10 and 50%, inclusive, of organic solvent.
 26. The composition according to claim 24, comprising between 10 and 25%, inclusive, of organic solvent.
 27. The composition according to claim 24, comprising between 25 and 60%, inclusive, of propellant gas.
 28. The composition according to claim 24, comprising between 30 and 50%, inclusive, of propellant gas.
 29. A composition comprising: a) Lactic acid/ethylene glycol P(MIS-EG)-dimethylolpropanoic acid (DMPA)-isophorone-diisocyanate polyester polycondensate; b) a polydimethylsiloxane onto which is grafted, via a thiopropylene connecting chain, mixed polymer units of poly(meth)acrylic acid and polybutyl (meth)acrylate ester; c) Aminomethyipropanol; d) Ethanol; e) Dimethyl ether; and f) Demineralized water.
 30. The composition according to claim 29, comprising: a) 4%, by weight, lactic acid/ethylene glycol P(MIS-EG)-dimethylolpropanoic acid (DMPA)-isophorone-diisocyanate polyester polycondensate; b) 0.2%, by weight, polydimethylsiloxane onto which is grafted, via a thiopropylene connecting chain, mixed polymer units of poly(meth)acrylic acid and polybutyl (meth)acrylate ester; c) a sufficient amount of aminomethylpropanol to adjust the composition to a neutral pH; d) 15%, by weight, ethanol; e) 35%, by weight, dimethyl ether; and f) a sufficient amount of demineralized water to adjust the total weight to 100%.
 31. An aerosol device comprising a container containing the composition according to claim 24, and a means for distributing the composition.
 32. The composition according to claim 1, further comprising at least one cosmetic additive chosen from fatty substances, thickeners, softeners, anti-foaming agents, moisturizers, antiperspirants, basifying agents, dyes, pigments, fragrances, preserving agents, surfactants, hydrocarbon-based polymers, additional volatile and non-volatile silicones, proteins, and vitamins.
 33. The composition according to claim 1, containing at least one fixing polymer chosen from nonionic, cationic, anionic, and amphoteric fixing polymers.
 34. A process for shaping or maintaining a hairstyle, said process comprising applying to hair a composition comprising in a relative proportion by weight, relative to the total weight of the composition: (a) from 0.1 to 20%, inclusive, of a polycondensate comprising at least one sequence chosen from polyurethanes and polyureas, (b) from 0.01 to 20%, inclusive, of at least one silicone chosen from partially and totally neutralized silicone compounds comprising at least one carboxylic functional group and salts thereof.
 35. A process for manufacturing at least one hair care product for maintaining or shaping a hairstyle, said process comprising including in said hair product a composition comprising in a relative proportion by weight, relative to the total weight of the composition: (a) from 0.1 to 20%, inclusive, of a polycondensate comprising at least one sequence chosen from polyurethanes and polyureas, (b) from 0.01 to 20%, inclusive, of at least one silicone chosen from partially and totally neutralized silicone compounds comprising at least one carboxylic functional group and salts thereof. 